CA2064135A1 - Process for preparing hindered amine light stabilizers - Google Patents
Process for preparing hindered amine light stabilizersInfo
- Publication number
- CA2064135A1 CA2064135A1 CA002064135A CA2064135A CA2064135A1 CA 2064135 A1 CA2064135 A1 CA 2064135A1 CA 002064135 A CA002064135 A CA 002064135A CA 2064135 A CA2064135 A CA 2064135A CA 2064135 A1 CA2064135 A1 CA 2064135A1
- Authority
- CA
- Canada
- Prior art keywords
- process according
- dicarboxylic acid
- acid ester
- hydroxypiperidine
- basic inorganic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 150000001412 amines Chemical class 0.000 title claims abstract description 7
- 239000004611 light stabiliser Substances 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- -1 alkyl substituted-4-hydroxypiperidine Chemical class 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 26
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 18
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 18
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 18
- 229940014772 dimethyl sebacate Drugs 0.000 claims description 13
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 3
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 claims description 2
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 2
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 2
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- KKZZSTCINUMTGD-UHFFFAOYSA-N 1,2,2,3-tetramethylpiperidin-4-ol Chemical compound CC1C(O)CCN(C)C1(C)C KKZZSTCINUMTGD-UHFFFAOYSA-N 0.000 claims 1
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims 1
- 150000001408 amides Chemical class 0.000 claims 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 claims 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 9
- 150000005690 diesters Chemical class 0.000 description 7
- 238000005809 transesterification reaction Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- VDVUCLWJZJHFAV-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-ol Chemical compound CC1(C)CC(O)CC(C)(C)N1 VDVUCLWJZJHFAV-UHFFFAOYSA-N 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 238000013019 agitation Methods 0.000 description 4
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- LKPFBGKZCCBZDK-UHFFFAOYSA-N n-hydroxypiperidine Chemical class ON1CCCCC1 LKPFBGKZCCBZDK-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229940116351 sebacate Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- UFCONGYNRWGVGH-UHFFFAOYSA-N 1-hydroxy-2,2,3,3-tetramethylpiperidine Chemical compound CC1(C)CCCN(O)C1(C)C UFCONGYNRWGVGH-UHFFFAOYSA-N 0.000 description 1
- RALRVIPTUXSBPO-UHFFFAOYSA-N 4-[4-chloro-3-(trifluoromethyl)phenyl]piperidin-4-ol Chemical compound C=1C=C(Cl)C(C(F)(F)F)=CC=1C1(O)CCNCC1 RALRVIPTUXSBPO-UHFFFAOYSA-N 0.000 description 1
- 101100448208 Human herpesvirus 6B (strain Z29) U69 gene Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PLOSSHSFATUNTF-UHFFFAOYSA-N [K]C1=CC=CC=C1 Chemical compound [K]C1=CC=CC=C1 PLOSSHSFATUNTF-UHFFFAOYSA-N 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 125000004482 piperidin-4-yl group Chemical group N1CCC(CC1)* 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KSMWLICLECSXMI-UHFFFAOYSA-N sodium;benzene Chemical compound [Na+].C1=CC=[C-]C=C1 KSMWLICLECSXMI-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D211/40—Oxygen atoms
- C07D211/44—Oxygen atoms attached in position 4
- C07D211/46—Oxygen atoms attached in position 4 having a hydrogen atom as the second substituent in position 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Investigation Of Foundation Soil And Reinforcement Of Foundation Soil By Compacting Or Drainage (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Breeding Of Plants And Reproduction By Means Of Culturing (AREA)
- Steroid Compounds (AREA)
- Measurement Of Radiation (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Abstract
PROCESS FOR PREPARING HINDERED
AMINE LIGHT STABILIZERS
ABSTRACT OF THE DISCLOSURE
Disclosed is a process for the preparation of hindered amine light stabilizers by reacting (a) an alkyl substituted-4-hydroxypiperidine with (b) a dicarboxylic acid ester, in the presence of a catalyst system comprising a basic inorganic compound and a polar aprotic organic compound.
AMINE LIGHT STABILIZERS
ABSTRACT OF THE DISCLOSURE
Disclosed is a process for the preparation of hindered amine light stabilizers by reacting (a) an alkyl substituted-4-hydroxypiperidine with (b) a dicarboxylic acid ester, in the presence of a catalyst system comprising a basic inorganic compound and a polar aprotic organic compound.
Description
2 ~ 5 ~
Case 8008 This invention relates to a process for the preparation of diesters of an alkyl substituted-4-hydroxy-piperidine compound from certain organic esters. More particularly this invention relates to a process for preparing diesters of an alkyl substituted-4-hydroxy-piperidine compound from dicarboxylic acid esters using a catalyst system comprising a basic inorganic compound and a polar aprotic organic compound.
Hindered amine light stabilizers (HALS) based on diesters of bis(substituted-piperidine) are known and are prepared by various methods. One method oP preparation is transesterification of a dicarboxylic acid ester by reacting a dicarboxylic acid ester, such as dimethyl-sebacate, with a substituted-4-hydroxypiperidine in the presence of a catalyst, such as an alkali metal amide, in the absence or presence of an inert solvent, such as toluene, to form the diester of the piperidine alcohol employed and methanol as the by-product.
For example, U.S. 4,021,432 describes the transesterification of dicarboxylic acid esters in the absence or presence of an inert solvent, such as benzene, toluene or xylene, with a substituted piperidinol compound in the presence of a transesterification catalyst, an alkali metal amide such as lithium amide, whereby the al~ohol produced in the reaction is removed. However,'the total reaction time is from about 4 to about 7 hours.
In U.SO 4,461,898 mixtures of esters of polyalkyl-piperidine derivatives are prepare~ by reacting 2 mols of a piperidinol wlth 0.9 to 1.3 mols of a diester, in the melt, at between 100 and 145C, in ~he presance of an alkali metal amide, preferably lithium amide, as a catalyst. After the reaction has started, the alcohol formed is removed by distillation, ~irst at atmospheric pressure, and then under vacuum for an additional 2 to 3 hours.
,, ,, -,,, - - - , ., . . :
It has now been found that by carrying out the transesterification of a diester with an alcohol in the presence of a catalyst system containing a polar aprotic solvent, in addition to the basic inorganic compound, provides higher conversion yields of the desired diester in shorter reaction times.
Accordingly, the present invention provides a process for preparing hindered amine light stabilizers by reacting (a) an alkyl substituted-4-hydroxypiperidine having the following ge~eral formula:
OH
H3C ~CH3 R ~ H2C ¦ CH2R
H
where R' is hydrogen or methyl, with tb) a dicarboxylic acid ester having the following general formula:
O O
R"-O-C-(CH2)o C-O-RI"
where R" and R"' are a Cl-C~ linear or branched alkyl, a C5-CI2 cycloalkyl, a C6~CI2 aryl, or a ~-CI2 alkaryl or aralkyl and may be the same or di~ferent, and n is a number from 1-12, in the presence of a basic inorganic compound/polar aprotic organic compound catalyst system, at a temperature from 80 to 165C
and under vacuum or under a flow of an inert gas at atmospheric pressure, wherein the alkyl substituted-4-hydroxypiperidine is present in an amount of ~rom 2 to 3.2 moles per mole of dicarboxylic acid ester.
1 3 ~
The preferred alkyl substituted-4-hydroxypiperidine compound useful in the practice of the present invention is 2,2,~,6-tetramethyl-4-hydroxypiperidine. The alkyl substituted-4-hydroxypiperidine is present in an amount of from ~ to 3.2 moles per mole of dicarboxylic acid ester used.
Preferably, the alkyl substituted-4-hydroxy- piperidine is present in an amount of from 2.2 to 3 moles per mole of dicarboxylic acid ester.
Suitable dicarboxylic acid esters useful in the present invention are those derived from malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic or 1, 12-dodecanedoic acid. Preferred is the ester of sebacic, and most preferred is dim thylsebacate (DMS).
The basic inorganic compounds useful in the practice of this invention are alkali metal compounds, such as alkali metal hydride, alkali metal hydroxides, alkali metal alkoxides, alkali metal amides and alkali metal alkyl amides.
Alkali metals for the basic compounds include lithium, sodium and potassium. Examples of the basic inorganic compounds useful in the present invention are lithium hydride, sodium hydride~ lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium methoxide, sodium methoxide, lithium methoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium tert-butoxide, sodium tert-butoxide, n-butyllithium, phenyl potassium~ phenyl sodium, lithium amide, potassium amide and lithium diisopropyl amide.
Preferred is lithium amide. The basic inorganic compound is typically present in an amount from about 1 to 30 mole % per mole of dicarboxylic acid ester used. Preferably, the basic inorganic compound is present in an amount of from about 2 to 15 mole %, and most preferably, from 5 to 7 mole % per mole of dicarboxylic acid ester.
,.,.., :,, : ~
2 ~ 3 ~
In order for a polar aprotic organic compound to be useful as a co-catalyst in the practice of this invention, it must h~ve sufficient polarity to dissolve the particular ingredients employed at the reaction temperature used and it must be capable of complexation with the metal ion of the basic inorganic compound used. Such polar aprotic organic compounds include N-methylpyrrolidinone (NMP), 1,2-dimethoxybenzene (DMB), N,N-dimethylacetamide (DMAC), hexamethyltriphosphoramide, tetramethylenesulfone, tetraethylene glycol dimethyl ether, ethylene glycol dimethylether, dimethylaminopyridine (DMAP), N,N,N',N'-tetramethyl-ethylenediamine (TMEDA) and l,3-dimethyl-2-imidazolidinone (DMI). Dimethylsulfoxide (DMSO) and crown ethers, such as 12-crown-4, can also be used as the solvent and co-catalyst and are within the broadest aspects of the invention. However, crown ethers are toxic and may leave impurities in the final products making them unacceptable for use in the manufacture of plastic articles to be used in contact with food, medicines, pharmaceuticals and othQr materials which are eaten, taken orally or intravenously or topically applied. NMP, DMI, DMB and DMAC are preferred, with DMB being the most preferred. The co-catalyst is present in an amount of from 5 to 20 wt. %, preferably 7 to lZ wt. %, based on the total reactants.
According to the process of this invention, an alkyl substituted-4-hydroxypiperidine of the formula described above, is reacted with a dicar~oxylic acid ester of the - ~ormula described above, in the presence of a polar aprotic organic compound at a temperature of from 80-110C. The basic inorganic compound is added and the reaction mixture is heated to a temperature of from 145-165C while continuously sparging with an inert gas, such as nitrogen, at atmospheric pressure or under vacuum. The inert gas or vacuum facilitates 2 ~ 6 413 ~
the removal of the by-product. Preferably the process is carried out under a flow of inert gas at atmospheric pressure.
As used in the present invention, the term "by-product"
refers to the alkanol formed during the transesterification synthesis, and "side-product" refers to any product other than the desired product which may be formed during the transesterification synthesis.
The order of addition of the polar aprotic organic compound and the basic inorganic compound to the reaction medium containing the ester and alcohol is not critical, since the reaction between reactants does not start until all of the reactants are present. The basic inorganic compound can be introduced into the reaction medium before the polar aprotic organic compound. Preferably, the polar aprotic organic compound is added to the reaction mixture first, in order to decrease the viscosity of the reaction mixture.
When sparging with an inert gas, such as nitro~en, in the practice of this invention, the sparging is done at a flow rate o~ from 0.2 L/min. to 1 Llmin., preferably from 0.5 to 1 L/min., most preferably at a low rate of about 0.5 L/min., at ambient pressure.
When the removal of the by-product is carried out under a v~cuum, the pressure must be low enough to effectively remove the by-product. The pressure can be from 1 mmHg to 200 mmHg, preferably from 30 to ~50 mmHg. Also, solvent refluxation plays an important role when the vacuum process is us~d, in that it aids in the removal of the by-product and accelerates the transesterification reaction.
Most preferably, the reaction mixture is rapidly agitated during the removal of the by-product to form homogeneous mixture thereby preventing the trapping of the by-product within the reaction medium which is somewhat viscous. The reaction is typically agitated from about ~50 rpm to about 2 ~ J ~
2000 rpm in a lab scale reaction. In a commercial scale process, typical commercial turbine mixers would be used to provide sufficiently rapid mixing.
Once the by-product has been removed, the reaction medium is then neutralized with an acid, such as glacial acetic acid, at a temperature of from 100-110C. After about 5-25 minutes, the reaction mass is crystallized from methanol and water to yield the final product.
The temperature range for carrying out the reaction of the present invention i5 from 80-165C, preferably from 100-155C.
The present invention is illustrated in greater detail by the examples o~ the invention set forth below.
All parts and percentages are by weight unless otherwise indicated.
The organic diester compounds were analyzed by gas chromatography u~ing a Hewlett-Packard Model 5890 Gas Ch~omatograph and a Hewlett-Packard Model 3396A for integration and data handling. The column was a 6' x 1/8" OD
stainless steel column packed with 3% SE-54 on 80-100 mesh chromosorb, with a thermal conductivity detector. The column oven was programmed from 100C to 320C at 10C/min. and held at the upper limit for 10 minutes. The composition was determined by area percent calculation.
Example_l To a reaction vessel equipped with a mechanical stirrer, a thermometer, a condenser maintained at 70C, a trap and nitrogen sparge tube are added dimethylsebacate (25 g, lQ9 mmoles), 2,2,6,6-tetramethyl-4-hydroxypiperdine (34 g, 217 mmoles~ and N-methylpyrrolidinone (7 ml) and heated to 100C.
Then lithium amide (0.124 g, 5.4 mmoles) is added with agitation and the reaction mixture is heated to 150-155C for .
2 0 ~
Case 8008 This invention relates to a process for the preparation of diesters of an alkyl substituted-4-hydroxy-piperidine compound from certain organic esters. More particularly this invention relates to a process for preparing diesters of an alkyl substituted-4-hydroxy-piperidine compound from dicarboxylic acid esters using a catalyst system comprising a basic inorganic compound and a polar aprotic organic compound.
Hindered amine light stabilizers (HALS) based on diesters of bis(substituted-piperidine) are known and are prepared by various methods. One method oP preparation is transesterification of a dicarboxylic acid ester by reacting a dicarboxylic acid ester, such as dimethyl-sebacate, with a substituted-4-hydroxypiperidine in the presence of a catalyst, such as an alkali metal amide, in the absence or presence of an inert solvent, such as toluene, to form the diester of the piperidine alcohol employed and methanol as the by-product.
For example, U.S. 4,021,432 describes the transesterification of dicarboxylic acid esters in the absence or presence of an inert solvent, such as benzene, toluene or xylene, with a substituted piperidinol compound in the presence of a transesterification catalyst, an alkali metal amide such as lithium amide, whereby the al~ohol produced in the reaction is removed. However,'the total reaction time is from about 4 to about 7 hours.
In U.SO 4,461,898 mixtures of esters of polyalkyl-piperidine derivatives are prepare~ by reacting 2 mols of a piperidinol wlth 0.9 to 1.3 mols of a diester, in the melt, at between 100 and 145C, in ~he presance of an alkali metal amide, preferably lithium amide, as a catalyst. After the reaction has started, the alcohol formed is removed by distillation, ~irst at atmospheric pressure, and then under vacuum for an additional 2 to 3 hours.
,, ,, -,,, - - - , ., . . :
It has now been found that by carrying out the transesterification of a diester with an alcohol in the presence of a catalyst system containing a polar aprotic solvent, in addition to the basic inorganic compound, provides higher conversion yields of the desired diester in shorter reaction times.
Accordingly, the present invention provides a process for preparing hindered amine light stabilizers by reacting (a) an alkyl substituted-4-hydroxypiperidine having the following ge~eral formula:
OH
H3C ~CH3 R ~ H2C ¦ CH2R
H
where R' is hydrogen or methyl, with tb) a dicarboxylic acid ester having the following general formula:
O O
R"-O-C-(CH2)o C-O-RI"
where R" and R"' are a Cl-C~ linear or branched alkyl, a C5-CI2 cycloalkyl, a C6~CI2 aryl, or a ~-CI2 alkaryl or aralkyl and may be the same or di~ferent, and n is a number from 1-12, in the presence of a basic inorganic compound/polar aprotic organic compound catalyst system, at a temperature from 80 to 165C
and under vacuum or under a flow of an inert gas at atmospheric pressure, wherein the alkyl substituted-4-hydroxypiperidine is present in an amount of ~rom 2 to 3.2 moles per mole of dicarboxylic acid ester.
1 3 ~
The preferred alkyl substituted-4-hydroxypiperidine compound useful in the practice of the present invention is 2,2,~,6-tetramethyl-4-hydroxypiperidine. The alkyl substituted-4-hydroxypiperidine is present in an amount of from ~ to 3.2 moles per mole of dicarboxylic acid ester used.
Preferably, the alkyl substituted-4-hydroxy- piperidine is present in an amount of from 2.2 to 3 moles per mole of dicarboxylic acid ester.
Suitable dicarboxylic acid esters useful in the present invention are those derived from malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic or 1, 12-dodecanedoic acid. Preferred is the ester of sebacic, and most preferred is dim thylsebacate (DMS).
The basic inorganic compounds useful in the practice of this invention are alkali metal compounds, such as alkali metal hydride, alkali metal hydroxides, alkali metal alkoxides, alkali metal amides and alkali metal alkyl amides.
Alkali metals for the basic compounds include lithium, sodium and potassium. Examples of the basic inorganic compounds useful in the present invention are lithium hydride, sodium hydride~ lithium hydroxide, sodium hydroxide, potassium hydroxide, potassium methoxide, sodium methoxide, lithium methoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium tert-butoxide, sodium tert-butoxide, n-butyllithium, phenyl potassium~ phenyl sodium, lithium amide, potassium amide and lithium diisopropyl amide.
Preferred is lithium amide. The basic inorganic compound is typically present in an amount from about 1 to 30 mole % per mole of dicarboxylic acid ester used. Preferably, the basic inorganic compound is present in an amount of from about 2 to 15 mole %, and most preferably, from 5 to 7 mole % per mole of dicarboxylic acid ester.
,.,.., :,, : ~
2 ~ 3 ~
In order for a polar aprotic organic compound to be useful as a co-catalyst in the practice of this invention, it must h~ve sufficient polarity to dissolve the particular ingredients employed at the reaction temperature used and it must be capable of complexation with the metal ion of the basic inorganic compound used. Such polar aprotic organic compounds include N-methylpyrrolidinone (NMP), 1,2-dimethoxybenzene (DMB), N,N-dimethylacetamide (DMAC), hexamethyltriphosphoramide, tetramethylenesulfone, tetraethylene glycol dimethyl ether, ethylene glycol dimethylether, dimethylaminopyridine (DMAP), N,N,N',N'-tetramethyl-ethylenediamine (TMEDA) and l,3-dimethyl-2-imidazolidinone (DMI). Dimethylsulfoxide (DMSO) and crown ethers, such as 12-crown-4, can also be used as the solvent and co-catalyst and are within the broadest aspects of the invention. However, crown ethers are toxic and may leave impurities in the final products making them unacceptable for use in the manufacture of plastic articles to be used in contact with food, medicines, pharmaceuticals and othQr materials which are eaten, taken orally or intravenously or topically applied. NMP, DMI, DMB and DMAC are preferred, with DMB being the most preferred. The co-catalyst is present in an amount of from 5 to 20 wt. %, preferably 7 to lZ wt. %, based on the total reactants.
According to the process of this invention, an alkyl substituted-4-hydroxypiperidine of the formula described above, is reacted with a dicar~oxylic acid ester of the - ~ormula described above, in the presence of a polar aprotic organic compound at a temperature of from 80-110C. The basic inorganic compound is added and the reaction mixture is heated to a temperature of from 145-165C while continuously sparging with an inert gas, such as nitrogen, at atmospheric pressure or under vacuum. The inert gas or vacuum facilitates 2 ~ 6 413 ~
the removal of the by-product. Preferably the process is carried out under a flow of inert gas at atmospheric pressure.
As used in the present invention, the term "by-product"
refers to the alkanol formed during the transesterification synthesis, and "side-product" refers to any product other than the desired product which may be formed during the transesterification synthesis.
The order of addition of the polar aprotic organic compound and the basic inorganic compound to the reaction medium containing the ester and alcohol is not critical, since the reaction between reactants does not start until all of the reactants are present. The basic inorganic compound can be introduced into the reaction medium before the polar aprotic organic compound. Preferably, the polar aprotic organic compound is added to the reaction mixture first, in order to decrease the viscosity of the reaction mixture.
When sparging with an inert gas, such as nitro~en, in the practice of this invention, the sparging is done at a flow rate o~ from 0.2 L/min. to 1 Llmin., preferably from 0.5 to 1 L/min., most preferably at a low rate of about 0.5 L/min., at ambient pressure.
When the removal of the by-product is carried out under a v~cuum, the pressure must be low enough to effectively remove the by-product. The pressure can be from 1 mmHg to 200 mmHg, preferably from 30 to ~50 mmHg. Also, solvent refluxation plays an important role when the vacuum process is us~d, in that it aids in the removal of the by-product and accelerates the transesterification reaction.
Most preferably, the reaction mixture is rapidly agitated during the removal of the by-product to form homogeneous mixture thereby preventing the trapping of the by-product within the reaction medium which is somewhat viscous. The reaction is typically agitated from about ~50 rpm to about 2 ~ J ~
2000 rpm in a lab scale reaction. In a commercial scale process, typical commercial turbine mixers would be used to provide sufficiently rapid mixing.
Once the by-product has been removed, the reaction medium is then neutralized with an acid, such as glacial acetic acid, at a temperature of from 100-110C. After about 5-25 minutes, the reaction mass is crystallized from methanol and water to yield the final product.
The temperature range for carrying out the reaction of the present invention i5 from 80-165C, preferably from 100-155C.
The present invention is illustrated in greater detail by the examples o~ the invention set forth below.
All parts and percentages are by weight unless otherwise indicated.
The organic diester compounds were analyzed by gas chromatography u~ing a Hewlett-Packard Model 5890 Gas Ch~omatograph and a Hewlett-Packard Model 3396A for integration and data handling. The column was a 6' x 1/8" OD
stainless steel column packed with 3% SE-54 on 80-100 mesh chromosorb, with a thermal conductivity detector. The column oven was programmed from 100C to 320C at 10C/min. and held at the upper limit for 10 minutes. The composition was determined by area percent calculation.
Example_l To a reaction vessel equipped with a mechanical stirrer, a thermometer, a condenser maintained at 70C, a trap and nitrogen sparge tube are added dimethylsebacate (25 g, lQ9 mmoles), 2,2,6,6-tetramethyl-4-hydroxypiperdine (34 g, 217 mmoles~ and N-methylpyrrolidinone (7 ml) and heated to 100C.
Then lithium amide (0.124 g, 5.4 mmoles) is added with agitation and the reaction mixture is heated to 150-155C for .
2 0 ~
3 hours at atmosphere pressure. During this period, nitrogen is continuously introduced subsurface at a rate of 0.5 L/min.
to remove the generated methanol. The completed reaction mass is then cooled down to 100C and neutralized with glacial acetic acid. Analysis by gas chromatography indicated that 99% of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate is obtained, based on the dimethylsebacate.
Control To a reaction vessel equipped with a mechanical stirrer, a thermometer, a condenser maintained at 70C and a nitrogen sparge tube are added dimethylsebacate (23 g, 100 mmoles) and 2,2,6,6-tetramethyl-4-hydroxy-piperidine (31.4 g, 200 mmoles) and heated to 100C. Then lithium amide (0.124 g, 5 mmoles) is added with agitation and the reaction mixture is heated to 150C while nitrogen is continuously introduced subsurface (0.5 L/min.) to remove the generated me~hanol. Cleaning of the condenser was necessary from time to time due to the sublimation of the tetramethylhydroxypiperidine starting material on the condenser. After approximateiy 4.5 hours the reaction mixture was stopped and the reaction crude is cooled to 100C and neutralized with glacial acetic acid. Analysis by, gas chromatography indicated that a mixture of 89~
bis(2,2,6,6-tetramethyl~4-piperidinyl)sebacate and 11% of the half-ester, methyl(2,2,6,6~tetramethyl-4-piperidinyl)-sebacate i obtained, based on the dimethylsebacate.
Example 2 To a reaction vessel equipped with a mechanical stirrer, a thermometer, a condenser maintained at 70C, a trap and nitrogen sparge tube`are added dimethylsebacate (25 g, 109 30 mmoles), 2,2,6,6-tetramethyl-4-hydroxypiperidine (37.5 g, 239 mmoles) and N-methylpyrrolidinone (7 ml) and heated to 100C.
",,, ,~,,,, . :
' "
' - , ~a~l3~
Then lithium amide (0.124 g, 5.4 mmoles~ is added with agitation and the reaction mixture is heated to 150 155C for 3 hours at atmospheric pressure. During this period, nitrogen is continuously introduced subsurface at a rate of 0.5 L/min.
to remove the generated methanol. The completed reaction mass is then cooled down to 100C and neutralized with glacial acetic acid. Analysis by gas chromatography indicated that 99% of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate is obtained, based on the dimethylsebacate.
Example 3 The procedure and ingredients of Example 2 are used except that 7 ml of dimethoxybenzene is used instead of N-methylpyrrolidinone. After 3 hours, analysis by gas chromatography indicated that 99% of bis(2,2,6,6-tetra-methyl 4-piperidinyl3sebacate is obtained, based on the dimethyl sebacate.
Example 4 To a reaction vessel equipped with a mechanical stirrer, a thermometer, a condenser maintained at 70C, a trap and a nitrogen sparge tube are added dimethylsebacate (14.0 g, 61 mmole), 2,2,6,6-tetramethyl-4-hydroxypiperidine (25 g, 158 mmole) and N-metbylpyrrolidinone (5 ml~ and heated to 100C.
Lithium amide (0.07 g, 3 mmole) was then added and the reaction was heated to 150-155 C for 3 hours. During this period, nitrogen is continuously introduced subsurface (0.5 ~/min.) to remove the generated methanol. The reaction was stopped and the reaction crude was cooled to 100C and neutralized with gacial acetic acid. Analysis by gas chroma~ography indicated that 99% of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate is obtained, based on the dimethylsebacate.
, . . . .
.
2 ~
Example 5 To a reaction vessel equipped with a mechanical stirrer, a thermometer, a condenser maintained at 70C, a trap and a nitrogen inlet are added dimethylsebacate (11.5 g, 50 mmole), 2,2,6,6-tetramethyl-4-hydroxypiperidine (23.6 g, 150 mmole) and N-methylpyrrolidinone (4 g) and heated to 100C with stirring under a nitrogen blanket. Then lithium amide (0.020 g, 0.87 mmoles) was added to the reaction mixture. With agitation and under a vacuum of 30 mm Hg, the reaction is heated to 105C for 3.5 hours and generated methanol is removed. The reaction was stopped and the reaction crude was cooled to 100C and neutralized with glacial acetic acid.
Analysis by gas chromatography indicated that 95% of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate i5 obtained, based on the dimethylsebacate.
The products produced by the process of the present invention are known and can be used as U.V. hindered amine light stabilizers in materials which are subject to degradation, such as plastics, rubbers and other polymers.
Other features, advantages and embodiments of the invention disclosed herein will be readily apparent to those exercising ordinary skill after reading the foregoing disclosures. In this regard, while specific embodiments of the invention have been described in considerable detail, variations and modifications of these embodiments can be effected without departing from the spirit and $cope of ~he invention as described and claimed~
.. . .
to remove the generated methanol. The completed reaction mass is then cooled down to 100C and neutralized with glacial acetic acid. Analysis by gas chromatography indicated that 99% of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate is obtained, based on the dimethylsebacate.
Control To a reaction vessel equipped with a mechanical stirrer, a thermometer, a condenser maintained at 70C and a nitrogen sparge tube are added dimethylsebacate (23 g, 100 mmoles) and 2,2,6,6-tetramethyl-4-hydroxy-piperidine (31.4 g, 200 mmoles) and heated to 100C. Then lithium amide (0.124 g, 5 mmoles) is added with agitation and the reaction mixture is heated to 150C while nitrogen is continuously introduced subsurface (0.5 L/min.) to remove the generated me~hanol. Cleaning of the condenser was necessary from time to time due to the sublimation of the tetramethylhydroxypiperidine starting material on the condenser. After approximateiy 4.5 hours the reaction mixture was stopped and the reaction crude is cooled to 100C and neutralized with glacial acetic acid. Analysis by, gas chromatography indicated that a mixture of 89~
bis(2,2,6,6-tetramethyl~4-piperidinyl)sebacate and 11% of the half-ester, methyl(2,2,6,6~tetramethyl-4-piperidinyl)-sebacate i obtained, based on the dimethylsebacate.
Example 2 To a reaction vessel equipped with a mechanical stirrer, a thermometer, a condenser maintained at 70C, a trap and nitrogen sparge tube`are added dimethylsebacate (25 g, 109 30 mmoles), 2,2,6,6-tetramethyl-4-hydroxypiperidine (37.5 g, 239 mmoles) and N-methylpyrrolidinone (7 ml) and heated to 100C.
",,, ,~,,,, . :
' "
' - , ~a~l3~
Then lithium amide (0.124 g, 5.4 mmoles~ is added with agitation and the reaction mixture is heated to 150 155C for 3 hours at atmospheric pressure. During this period, nitrogen is continuously introduced subsurface at a rate of 0.5 L/min.
to remove the generated methanol. The completed reaction mass is then cooled down to 100C and neutralized with glacial acetic acid. Analysis by gas chromatography indicated that 99% of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate is obtained, based on the dimethylsebacate.
Example 3 The procedure and ingredients of Example 2 are used except that 7 ml of dimethoxybenzene is used instead of N-methylpyrrolidinone. After 3 hours, analysis by gas chromatography indicated that 99% of bis(2,2,6,6-tetra-methyl 4-piperidinyl3sebacate is obtained, based on the dimethyl sebacate.
Example 4 To a reaction vessel equipped with a mechanical stirrer, a thermometer, a condenser maintained at 70C, a trap and a nitrogen sparge tube are added dimethylsebacate (14.0 g, 61 mmole), 2,2,6,6-tetramethyl-4-hydroxypiperidine (25 g, 158 mmole) and N-metbylpyrrolidinone (5 ml~ and heated to 100C.
Lithium amide (0.07 g, 3 mmole) was then added and the reaction was heated to 150-155 C for 3 hours. During this period, nitrogen is continuously introduced subsurface (0.5 ~/min.) to remove the generated methanol. The reaction was stopped and the reaction crude was cooled to 100C and neutralized with gacial acetic acid. Analysis by gas chroma~ography indicated that 99% of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate is obtained, based on the dimethylsebacate.
, . . . .
.
2 ~
Example 5 To a reaction vessel equipped with a mechanical stirrer, a thermometer, a condenser maintained at 70C, a trap and a nitrogen inlet are added dimethylsebacate (11.5 g, 50 mmole), 2,2,6,6-tetramethyl-4-hydroxypiperidine (23.6 g, 150 mmole) and N-methylpyrrolidinone (4 g) and heated to 100C with stirring under a nitrogen blanket. Then lithium amide (0.020 g, 0.87 mmoles) was added to the reaction mixture. With agitation and under a vacuum of 30 mm Hg, the reaction is heated to 105C for 3.5 hours and generated methanol is removed. The reaction was stopped and the reaction crude was cooled to 100C and neutralized with glacial acetic acid.
Analysis by gas chromatography indicated that 95% of bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate i5 obtained, based on the dimethylsebacate.
The products produced by the process of the present invention are known and can be used as U.V. hindered amine light stabilizers in materials which are subject to degradation, such as plastics, rubbers and other polymers.
Other features, advantages and embodiments of the invention disclosed herein will be readily apparent to those exercising ordinary skill after reading the foregoing disclosures. In this regard, while specific embodiments of the invention have been described in considerable detail, variations and modifications of these embodiments can be effected without departing from the spirit and $cope of ~he invention as described and claimed~
.. . .
Claims (17)
1. A process for preparing hindered amine light stabilizers by reacting (a) an alkyl substituted-4-hydroxy-piperidine having the following general formula:
where R' is hydrogen or methyl, with (b) a dicarboxylic acid ester of the formula:
where R" and R"' are a C1-C12 linear or branched alkyl, a C5-C12 cycloalkyl, a C6-C12 aryl or a C7-C12 alkaryl or aralkyl and may be the same or different, and n is a number from 1-12, in the presence of a polar aprotic organic compound and basic inorganic compound catalyst system, wherein a 2-1 to 3.2:1 mole ratio of alkyl substituted-4-hydroxypiperidine to dicarboxylic acid ester is used.
where R' is hydrogen or methyl, with (b) a dicarboxylic acid ester of the formula:
where R" and R"' are a C1-C12 linear or branched alkyl, a C5-C12 cycloalkyl, a C6-C12 aryl or a C7-C12 alkaryl or aralkyl and may be the same or different, and n is a number from 1-12, in the presence of a polar aprotic organic compound and basic inorganic compound catalyst system, wherein a 2-1 to 3.2:1 mole ratio of alkyl substituted-4-hydroxypiperidine to dicarboxylic acid ester is used.
2. The process according to claim 1, wherein (a) is 2,2 7 6,6 tetramethyl-4-hydroxypiperidine.
3. The process according to claim 1, wherein (b) is dimethylsebacate.
4. The process according to claim 1, wherein said polar aprotic organic compound is selected from the group consisting of N-methylpyrrolidinone, 1,2-dimethoxybenzene, N,N-dimethyl-acetamide, hexamethyltriphosphoramide, dimethylaminopyridine, tetramethylenesulfone, tetramethyl glycol dimethylether, ethylene glycol dimethylether, N,N,N',N'-tetramethylethyl-enediamine, 1,3-dimethyl-2-imidazolidinone, dimethylsulfoxide and 12-crown-4.
5. The process according to claim 4, wherein said polar aprotic organic compound is N-methylpyrrolidinone.
6. The process according to claim 4, wherein said polar aprotic organic compound is 1,2-dimethoxybenzene.
7. The process according to claim 1, wherein said basic inorganic compound is selected from the group consisting of alkali metal hydroxides, alkali metal alkoxides, alkali metal amides, alkali metal alkyl amides and alkali metal hydrides.
8. The process according to claim 7, wherein said basic inorganic compound is selected from the group consisting of potassium methoxide, sodium methoxide, lithium methoxide, potassium ethoxide, sodium ethoxide, lithium ethoxide, potassium-t-butoxide, sodium-t-butoxide, lithium amide, n-butyllithium amide, lithium diisopropyl amide, potassium amide, lithium hydride and sodium hydride.
9. The process according to claim 8, wherein said basic inorganic compound is lithium amide.
10. The process according to claim 1, wherein the reaction temperature is from 80-165°C.
11. The process according to claim 1 which is conducted under vacuum.
12. The process according to claim 1 which is conducted under a flow of an inert gas at atmospheric pressure.
13. The process according to claim, 1 wherein said basic inorganic compound is present in the amount of from 1 to 30 mole % per mole of dicarboxylic acid ester.
14. The process according to claim 1, wherein said basic inorganic compound is present in the amount of 5 to 7 mole % per mole of dicarboxylic acid ester.
15. The process according to claim 1, wherein the ratio of alkyl substituted-4-hydroxypiperidine to dicarboxylic acid ester is 2:1.
16. The process according to claim 1, wherein the ratio of alkyl substituted-4-hydroxypiperidine to dicarboxylic acid ester is 2.6:1.
17. The process according to claim 1, wherein the ratio of alkyl substituted-4-hydroxypiperidine to dicarboxylic acid ester is 3:1.
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GB2377709B (en) * | 1998-12-14 | 2003-06-18 | Ciba Sc Holding Ag | Sterically hindered amine compounds |
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CN101381477B (en) * | 2008-10-15 | 2011-04-27 | 天津大学 | Hindered amine light stabilizer and synthetic method thereof |
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-
1991
- 1991-04-24 US US07/690,760 patent/US5180830A/en not_active Expired - Fee Related
-
1992
- 1992-03-24 HU HU9200970A patent/HUT60718A/en unknown
- 1992-03-24 IL IL101357A patent/IL101357A0/en unknown
- 1992-03-26 CA CA002064135A patent/CA2064135A1/en not_active Abandoned
- 1992-04-02 ZA ZA922424A patent/ZA922424B/en unknown
- 1992-04-14 JP JP4094528A patent/JPH05148229A/en active Pending
- 1992-04-17 CN CN92102840A patent/CN1038677C/en not_active Expired - Fee Related
- 1992-04-22 BR BR929201470A patent/BR9201470A/en not_active Application Discontinuation
- 1992-04-22 KR KR1019920006722A patent/KR920019747A/en active IP Right Grant
- 1992-04-23 AT AT92106920T patent/ATE154928T1/en not_active IP Right Cessation
- 1992-04-23 RU SU925011466A patent/RU2036921C1/en active
- 1992-04-23 MX MX9201880A patent/MX9201880A/en not_active IP Right Cessation
- 1992-04-23 EP EP92106920A patent/EP0510625B1/en not_active Expired - Lifetime
- 1992-04-23 AU AU15058/92A patent/AU1505892A/en not_active Abandoned
- 1992-04-23 DE DE69220610T patent/DE69220610T2/en not_active Expired - Fee Related
- 1992-04-23 DK DK92106920.9T patent/DK0510625T3/en active
- 1992-04-24 CS CS921261A patent/CS126192A3/en unknown
- 1992-04-24 FI FI921851A patent/FI921851A/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
EP0510625B1 (en) | 1997-07-02 |
HU9200970D0 (en) | 1992-06-29 |
IL101357A0 (en) | 1992-11-15 |
CN1066064A (en) | 1992-11-11 |
KR920019747A (en) | 1992-11-19 |
MX9201880A (en) | 1992-10-01 |
RU2036921C1 (en) | 1995-06-09 |
FI921851A0 (en) | 1992-04-24 |
FI921851A (en) | 1992-10-25 |
DK0510625T3 (en) | 1997-07-21 |
BR9201470A (en) | 1992-12-01 |
CS126192A3 (en) | 1992-11-18 |
JPH05148229A (en) | 1993-06-15 |
AU1505892A (en) | 1992-10-29 |
ZA922424B (en) | 1992-12-30 |
DE69220610D1 (en) | 1997-08-07 |
DE69220610T2 (en) | 1997-12-18 |
EP0510625A1 (en) | 1992-10-28 |
US5180830A (en) | 1993-01-19 |
CN1038677C (en) | 1998-06-10 |
ATE154928T1 (en) | 1997-07-15 |
HUT60718A (en) | 1992-10-28 |
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Legal Events
Date | Code | Title | Description |
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EEER | Examination request | ||
FZDE | Discontinued |